186
Vol. 51, No. 2
raphy to give 22 (32.0 g, 84%, 2 steps) as colorless oil. IR (neat) 2982, 1720
Jϭ7.2 Hz), 7.13—7.29 (9H, m), 7.40—7.46 (2H, m), 7.54—7.57 (1H, m),
7.82—7.84 (2H, m). MS m/z (%) 366 (Mϩ, 4), 262 (42), 117 (91), 105 (71),
91 (100), 77 (39). Calcd for C22H19ClOS: M, 366.0844. Found: m/z
366.0843.
1
(CO), 1653 (CϭC), 1271, 1161, 699 cmϪ1; H-NMR d 1.27 (3H, t, Jϭ7.2
Hz), 3.52 (2H, dd, Jϭ6.7, 1.4 Hz), 4.18 (2H, q, Jϭ7.1 Hz), 5.81 (1H, dt, Jϭ
17.1, 1.5 Hz), 7.10 (1H, dt, Jϭ15.6, 6.9 Hz), 7.17—7.33 (5H, m). MS m/z
(%) 190 (Mϩ, 60), 162 (8), 145 (41), 117 (100), 91 (31), 28 (51). Calcd for
C12H14O2: M, 190.0993. Found: m/z 190.0989.
N-Phenyl-3-(p-chlorophenylthio)-4-phenylbutanamide (30): Colorless oil.
1
IR (neat) 3274 (NH), 2923, 1659 (CO), 1532, 1096, 752 cmϪ1; H-NMR d
2-(p-Chlorophenylthio)-4-phenylbutane (23) To
a solution of t-
2.09—2.16 (1H, m), 2.36—2.43 (1H, m), 2.83—2.94 (2H, m), 3.68 (1H, t,
Jϭ7.2 Hz), 7.04—7.56 (14H, m), 8.21 (1H, s). MS m/z (%) 381 (Mϩ, 23),
277 (99), 158 (42), 117 (41), 91 (100). Calcd for C22H20ClNOS: M,
381.0955. Found: m/z 381.0963.
BuMgCl (0.1 ml, 0.1 mmol) in 2 ml of THF at Ϫ78 °C was added dropwise
with stirring a solution of dithioacetal monoxide 8b (84.2 mg, 0.2 mmol) in
THF. After 5 min, to the reaction solution was added dropwise i-PrMgCl
(0.3 ml, 0.6 mmol) and the reaction mixture was warmed to room tempera-
ture. After 10 min, CuI (3.8 mg, 10 mol%)25 and CH3I (0.06 ml, 0.88 mmol)
were added to the flask. The reaction mixture was stirred for 60 min. The re-
action was quenched by sat. aq. NH4Cl and the whole was extracted with n-
hexane. The solution was dried over anhydrous MgSO4 and the solvent was
evaporated. The product was a mixture of 23 (28.4 mg, 51%) and 12a
Acknowledgments We thank Mr. Shinya Kikuchi for his technical as-
sistance. This work was supported by a Grant-in-Aid for Scientific Research
No. 11640545 from the Ministry of Education, Culture, Sports, Science and
Technology, Japan, which is gratefully acknowledged.
1
(13.1 mg, 25%). IR (neat) 2925, 1475, 1095, 1013, 819, 746, 699 cmϪ1; H-
References and Notes
NMR d 1.30 (3H, d, Jϭ6.7 Hz), 1.77—1.85 (1H, m), 1.87—1.94 (1H, m),
2.72—2.83 (2H, m), 3.15 (1H, sex, Jϭ6.7 Hz), 7.1—7.3 (9H, m). 13C-NMR
d 21.05 (1C, q), 33.10 (1C, t), 38.08 (1C, t), 42.74 (1C, t), 125.97 (1C, d),
128.43 (4C, d), 128.93 (2C, d), 132.82 (1C, d), 133.29 (2C, d), 133.58 (1C,
s), 141.45 (1C, s). MS m/z (%) 276 (Mϩ, 34), 262 (10), 144 (16), 132 (33),
117 (24), 91 (100). Calcd for C16H17ClS: M, 276.0739. Found: m/z
276.0741.
1) Block E., “Reactions of Organosulfur Compounds,” Academic Press,
New York, 1978, p. 47.
2) Corey E. J., Seebach D. J., J. Org. Chem., 31, 4097—4099 (1966).
3) Gilman H., Webb F. J., J. Am. Chem. Soc., 62, 987—988 (1940).
4) Gilman H., Webb F. J., J. Am. Chem. Soc., 71, 4062—4066 (1949).
5) Peterson D. J., J. Org. Chem., 32, 1717—1720 (1967).
6) Wakefield B. J., “Organomagnesium Methods in Organic Synthesis,”
Academic Press, London, 1995.
3-(p-Chlorophenylthio)-1,5-diphenylpentane (24): Colorless oil. IR (neat)
2926, 1496, 1475, 1454, 1095, 1013, 820, 746, 699 cmϪ1 1H-NMR d
;
7) Richey H. G., Jr., “Grignard Reagents New Developments,” John
Wiley, Chichesterr, 2000.
1.83—1.97 (4H, m), 2.77 (4H, t, Jϭ7.0 Hz), 3.01 (1H, quin, Jϭ6.5 Hz),
7.04—7.33 (14H, m). MS m/z (%) 366 (Mϩ, 47), 145 (20), 131 (46), 117
(14), 91 (100). Calcd for C23H23ClS: M, 366.1207. Found: m/z 366.1200.
2-(p-Chlorophenylthio)-1,4-diphenylbutane (25): Colorless oil. IR (neat)
8) Generation of 1-(methylthio)ethenylmagnesium chlorides (a-thioalkenyl
-
magnesium chloride) from the corresponding ketenedithioacetal
monoxides by ethylmagnesium chloride was known: Ogura K., Arai
K., Tsuchihashi G., Bull. Chem. Soc. Jpn., 55, 3669—3670 (1982).
9) Generation of the carbanion having oxygen (4: YϭO): Satoh T.,
Horiguchi K., Tetrahedron Lett., 36, 8235—8238 (1995).
10) Satoh T., Kobayashi S., Nakanishi S., Horiguchi K., Irisa S., Tetrahe-
dron, 55, 2515—2528 (1999).
3026, 2925, 1496, 1475, 1454, 1095, 1013, 745, 699 cmϪ1 1H-NMR d
;
1.75—1.82 (1H, m), 1.90—1.97 (1H, m), 2.71—2.77 (1H, m), 2.80—2.97
(3H, m), 3.24—3.29 (1H, m), 7.07—7.31 (14H, m). MS m/z (%) 352 (Mϩ,
32), 262 (3), 149 (11), 131 (20), 117 (92), 91 (100). Calcd for C22H21ClS:
M, 352.1052. Found: m/z 352.1061.
2-(p-Chlorophenylthio)-1-(p-methoxyphenyl)-4-phenylbutane (26): Col-
orless oil. IR (neat) 2919, 1509, 1475, 1245, 1094 cmϪ1; 1H-NMR d 1.72—
1.82 (1H, m), 1.88—1.97 (1H, m), 2.70—2.91 (1H, m), 3.20—3.26 (1H, m),
3.78 (3H, s), 6.77—6.82 (2H, m), 7.01—7.05 (2H, m), 7.07—7.10 (2H, m),
7.16—7.27 (7H, m). MS m/z (%) 382 (Mϩ, 47), 149 (15), 131 (32), 121
(83), 117 (100), 91 (93). Calcd for C23H23ClOS: M, 382.1156. Found: m/z
382.1148.
11) Generation of the carbanion having nitrogen (4: YϭN): Satoh T.,
Ozawa M., Takano K., Kudo M., Tetrahedron Lett., 39, 2345—2348
(1998).
12) Satoh T., Ozawa M., Takano K., Chyouma T., Okawa A., Tetrahedron,
56, 4415—4425 (2000).
13) Satoh T., Matsue R., Fujii T., Morikawa S., Tetrahedron Lett., 41,
6495—6499 (2000).
2-(p-Chlorophenylthio)-1,4-diphenyl-1-butanol (27): Diastereomeric mix-
ture; colorless oil. IR (neat) 3445 (OH), 3027, 2926, 1475, 1095, 1013, 746,
699 cmϪ1; 1H-NMR (more polar product) d 1.60—1.67 (1H, m), 1.76—1.83
(1H, m), 2.66 (1H, dt, Jϭ13.8, 8.2 Hz), 2.89—2.94 (1H, m), 3.11—3.15
(1H, m), 3.17 (1H, d, Jϭ2.5 Hz), 4.51 (1H, dd, Jϭ7.9, 2.5 Hz), 6.97 (2H, d,
Jϭ7.0 Hz), 7.14—7.35 (12H, m), 1H-NMR (less polar product) d 1.70—
1.78 (1H, m), 1.92—1.99 (1H, m), 2.61 (1H, dt, Jϭ13.8, 8.4 Hz), 2.66 (1H,
d, Jϭ2.8 Hz), 2.86—2.92 (1H, m), 3.27 (1H, dt, Jϭ10.1, 3.4 Hz), 4.76 (1H,
s), 6.99—7.01 (2H, m), 7.14—7.32 (12H, m). MS m/z (%) 368 (Mϩ, 6), 262
(74), 117 (98), 91 (100). Calcd for C22H21ClOS: M, 368.1002. Found: m/z
368.1009.
14) Satoh T., Matsue R., Fujii T., Morikawa S., Tetrahedron, 57, 3891—
3898 (2001).
15) Generation of the carbanion having a halogen (4: Xϭhalogen): Satoh
T., Takano K., Tetrahedron, 52, 2349—2358 (1996).
16) Satoh T., Takano K., Ota H., Someya H., Matsuda K., Koyama M.,
Tetrahedron, 54, 5557—5574 (1998).
17) Satoh T., Kurihara T., Fujita K., Tetrahedron, 57, 5369—5375 (2001).
18) Satoh T., Sakamoto T., Watanabe M., Tetrahedron Lett., 43, 2043—
2046 (2001).
19) A review for the chemistry of the sulfoxide-metal exchange reaction:
Satoh T., J. Syn. Org. Chem. Jpn., 54, 481—489 (1996).
20) Gutierrez C. G., Stringham R. A., Nitasaka T., Glasscock K. G., J.
Org. Chem., 45, 3393—3395 (1980).
21) Gutierrez C. G., Summerhays L. R., J. Org. Chem., 49, 5206—5213
(1984).
22) Watanabe Y., Araki T., Ueno Y., Endo T., Tetrahedron Lett., 72,
5385—5388 (1986).
23) Satoh T., Kubota K., Tetrahedron Lett., 41, 2121—2124 (2000).
24) Satoh T., Sugiyama S., Ota H., Tetrahedron Lett., 43, 3033—3036
(2002).
25) Wakefield B. J., “Organomagnesium Methods in Organic Synthesis,”
Academic Press, London, 1995, pp. 153—154.
4-(p-Chlorophenylthio)-2,2-dimethyl-6-phenyl-3-hexanol (28): Diastere-
omeric mixture; colorless oil. IR (neat) 3480 (OH), 2956, 1475, 1096, 1013,
1
821, 746, 700 cmϪ1; H-NMR (less polar product) d 0.78 (9H, s), 1.76—
1.84 (1H, m), 2.03 (1H, d, Jϭ4.6 Hz), 2.16—2.23 (1H, m), 2.79 (1H, dt,
Jϭ13.75, 8.5 Hz), 3.01—3.06 (1H, m), 3.23 (1H, dt, Jϭ10.6, 2.5 Hz), 3.37
(1H, d, Jϭ2.4 Hz), 7.26—7.31 (9H, m). MS m/z (%) 348 (Mϩ, 25), 262 (71),
144 (24), 118 (67), 117 (57), 91 (100). Calcd for C20H25ClOS: M, 348.1314.
Found: m/z 348.1316.
2-(p-Chlorophenylthio)-1,4-diphenyl-1-butanone (29): Colorless oil. IR
(neat) 2925, 1682 (CO), 1475, 1448, 1095, 1014, 746, 699 cmϪ1; 1H-NMR d
2.07—2.15 (1H, m), 2.29—2.36 (1H, m), 2.71—2.84 (2H, m), 4.37 (1H, t,